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Патент USA US2107508

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Patented Feb. 8, 1938
Alfred L. Rummelsburg, Wilmington, Del., assign
or to Hercules Powder Company, Wilmington,
Del., a corporation of Delaware
No Drawing. Application March 16, 1934,
Serial No. 715,941
19 Claims.
(Cl. 260-9912) ‘
oxygen. The bomb is then ?lled with hydrogen
genated abietyl derivatives and methods for ' to a pressure of about 1720 lbs. sq. in. Electric
their production.
heating'and agitation is started and about 3
In accordance with this invention it has been hours is required for the bomb to reach its maxi
This invention relates to sulphonated hydro
5 found possible to sulphonate various hydro
genated‘ abietyl derivatives, such as dihydro
abietyl alcohol, tetrahydroabietyl alcohol, etc., or
mixtures thereof, and the corresponding halides
or their mixtures, by treating, for example, the
10 alcohols with any of the known sulphonating
agents, such as sulphuric acid, sulphur trioxide,
mum temperature of 275° C. as follows:
Time Temp. g‘i?lsllége
~ 10
chlorsulphonic acid, acetyl sulphuric acid, etc.,
or by treating,'for example, the halides with a sul
The hydrogenated abietyl derivatives referred to
in the speci?cation and claims as suitable for
sulphonation may accordingly be represented as
C19H31CH2X, C19H33CH2X, or mixtures thereof,
25 where X is OH, Cl, Br, NHz, or other functional
group replaceable in sulphonation by the sul
phate or sulphonate group.
Dihydro- and tetrahydroabietyl alcohols may
be obtained by catalytic hydrogenation of alkyl
30 abietates, or alkyl esters of rosin, crude or re
By the term “hydrogenated abietyl alcohol” is
' hydroabietyl alcohol), related to abietic acid,
2 O C19H29COOH, or a mixture of these two alcohols.
meant a primary alcohol, C19H31CH2OH (di
hydroabietyl alcohol) or C19H33CH2OH (tetra
° C'.
phite, as sodium sulphite, sodium acid sulphite,
15 etc.
Typical run
Agitation and heating is stopped and the system 20
allowed to cool to 25° C. The pressure is then
#1000. The gas is bled off, and the product ex
tracted with ether, ?ltered from catalyst, and
the ether then evaporated. The product con
tains 89% hydrogenated abietyl alcohol.
The copper-chromium oxide catalyst is desir
ably prepared according to the method described
by Connor, Folkers and Adkins,_J. A. ‘(3.8. Vol.
54, pages 1139-40.
Pressure of reduction of the abietyl compound 30
fined, or the corresponding hydrogenated esters, “to the alcohol may range from about 50 to 2000
all as is more fully disclosed in the application
for United States patent Serial No. 604,859, filed
April 12, 1932, by Irvin W. Humphrey, or by
35 means of the action of sodium upon an alcohol
solution of hydrogenated methyl or ethyl able
tate according to the method described by Ru
zicka and Meyer, Helv. Chim. Acta 5, 581-93
(1922) for the unhydrogenated abietates. The
40 corresponding ‘halides, as, for example, dihydro
atmospheres, and temperature from about 1'75 to
350° C.
The hydrogenated abietyl alcohol may be puri
?ed, if desired, by means of fractional distilla- 35
tion at reduced pressure, distilling off a pre
liminary cut of say 5—l5% which may be low in
hydrogenated abietyl alcohol, depending upon
the conditions of hydrogenation and source of
raw material.
abietyl chloride and bromide, tetrahydroabietyl
The main portion of the hydrogenated abietyl
chloride and bromide, etc. may be produced by . ‘alcohol may be distilled under reduced pressure,
treating the alcohol with the desired hydrogen if desired, to improve its color and remove traces
halide, as hydrogen chloride, hydrogen bromide, of catalyst, if such be present. During the dis
45 etc., or with phosphorus tri- or pentachloride,
phosphorus tribromide, etc.
Thus, hydrogenated abietyl alcohol may be
_ produced from hydrogenated methyl abietate in
the following manner:
120 g. hydrogenated methyl abietate are placed
in a pressure bomb equipped with electric heat
ing, hydrogen inlet, agitator, and 'pyrometric
secondary. devices, 4 g. copper-chromium oxide
catalyst are added and H2 gas allowed to enter
55 and leave several times in order to ?ush out‘
tillation several cuts of the distillate may be 45
The raw material for conversion may, in place
of hydrogenated methyl abietate, be rosin, rosin
esters as methyl abietate, ethyl abietate, butyl
abietate, propyl abietate, etc., abietic acid, abietic 50
acid esters or other abietyl compounds contain
ing a group reducible to the primary alcohol
group, CI-IzOH.‘ The raw material may be hydro
genated to its dihydro or tetrahydro abietyl com
pound, or a mixture of the two, prior to reduc- 55
tion to hydrogenated abietyl alcohol. In event
The sulphonated hydrogenated abietyl deriva
tives produced in accordance with this invention
not partially hydrogenated in .a separate opera
are brownish-colored solids containing from 2 to
tion, prior to the reduction or the carboxyl group . 16% combined sulphur and are highly useful as
the unsaturated bonds in the raw materials are
I to the alcohol group, the latter procedure normal
ly results in a partial saturation of the unsat
urated bonds of the abietyl compound with hydro
gen. Thus, methyl abietate will yield dihydro
abietyl alcohol.
If desired, the abietyl compound may be isom
erized prior to its conversion to hydrogenated
abietyl alcohol by means of heat treatment at
temperatures of about 250-325° or by heating
with dilute acids at lower temperatures.
cludes broadly the treatment in any suitable man
Either gum‘ rosin or wood rosin may be em.
ployed for conversion to hydrogenated abietyl al
cohol. Other resin acids of similar structure may
be employed, or ‘their esters, in order to synthesize
various resin alcohols. 11' desired, the rosin prior
20 to conversion may be partially distilled under re
duced pressure separating a cut oi\say,;5-15%:
this procedure will increase the abietic acid con
tent of the residue which accordingly will yield a
hydrogenated abietyl alcohol oi’ higherv purity
than the original rosin.
dispersive, emulsifying, and wetting-out agents.
Their alkali salts, as for example, the sodium,
potassiumLor ammonium salts of these sulphona
tion products, are soluble in water; while their
salts with organic bases, as for example, pyri
dine, quinoline, triethanolami-ne, etc., are soluble
in petroleum and aromatic Chydrocarbons.
The method in accordance with this invention
requires no special form of apparatus and in
. If desired the wood or gum rosin may be re
?ned prior to conversion, as by distillation under
reduced pressure according to known procedures,
the distillate or one of its cuts being used as the
' source of hydrogenated abietyl alcohol._ The
rosin maylalso be given a prior re?ning by crystal
‘lization from a suitable solvent or by washing in
solution, as gasoline, with a substantially im
miscible color ‘body solvent as furfural or phenol
for‘ the removal of color bodies and other im
purities. It is to be realized that the crude prod
ucts of the above reactions, comprising mixtures
of_ the various hydrogenated abietyl alcohols,
may be sulphonated in accordance with this in
vention without substantial puri?cation. For
example, a technical grade or hydrogenated
abietyl alcohol comprising alcohols of varying de
grees of hydrogenation and obtained by hydro
‘genation as above described of alkyl abietates
may be treated in accordance with this lnven- '
tion without; further puri?cation. Such tech
. nical grades may have a total abietyl alcohol
content of about 50%, but desirably for treat
ment in accordance with this invention will con
tain from 80-95% abietyl alcohols. , The non-al
cohol content is probably a C19 cyclic hydrocarbon.
The products in accordance with this invention
willv comprise, depending upon the particular
vhydrogenated abietyl derivative and sulphonating
agent employed, various hydroabietyl sulphonates
and/or sulphates and mixtures thereof; The dis
ner ‘ of hydrogenated abietyl derivative with a 15
sulphonating agent.
Thus, for example, the
hydrogenated abietyl derivative, as an abietyl al
cohol, may be slowly added to the sulphonating
agent, as for example, concentrated sulphuric
acid, with vigorous agitation. The ratio of al
cohol to acid may be widely varied, for example,
from 1:0.3 to 1:50 parts by weight, and‘ the reac
tion temperature may be varied within wide lim
its, for example, from about —20° C. to about 200°
6., although a temperature or from about 10° C.
to about 40° C. is preferred. The agitation will
be continued after the addition of all-the alcohol
,until a test portion of the mixture is completely
soluble when dropped into water-about 6 to 20
hours at room temperature. The mixture is then 30
diluted with water while cooled and agitated to
give an acid concentration of 30 to 70%, The
free sulphonation product will separate as the
upper layer on standing and is puri?ed by being
dissolved in water, neutralized, salted out with,
for example, a saturated solution of sodium
chloride or sulphate, and dried.
If desired the sulphonating agent, as, for exam
ple, fuming sulphuric acid, may be added to the
hydrogenated abietyl derivative, for example, a 40
hydrogenated abietyl alcohol, dissolved in a'suit
able non-reactive solvent, such as ether, petroleum
ether, hexane, etc., or in a solvent such as acetic ‘
anhydride, glacial acetic acid, etc., which com,
bines with the sulphuric acid to form acetylsul 45
phuric acid, a sulphonating agent. The acid will
be added in excess, usually in considerable ex
cess, and upon completion of the reaction the
product may be obtained by washing the solvent
and excess acid away with a saturated salt so 50
lution if a water-soluble solvent, e. g. acetic acid,
is used, or by simple removal from a solvent in
which it is substantially insoluble, e. g. petrole
um ether. A further yield can be obtained by
evaporation of the solvent and recovery of the 55
product dissolved thereby. The product will be
tinction between the sulphonates and the sul
puri?ed as described above.
phates is purely technical. In the sulphateslthe
Where a non-alcohol, hydrogenated abietyl de
rivative, as for example, a hydrogenated abietyl
linkage to carbon is through an oxygen atom,
80., while in the sulphonates thelinkage to carbon is
directly through the sulphur atom. The process
in‘ accordance with this invention, especially
where only partially saturated abietyl deriva
tives are employed, may produce mixed sulpho
65 nates and sulphates since there are several reac
tive points in the abietyl radical besides the posi
tion occupied by the functional group, and ac
cordingly several di?erent reactions with the sul
phonating agent may take place. However, since
70 all,_ these sulphates, sulphonates, and mixtures
halide, is employed, the sulphonatingagent ‘will 60
desirably be a sulphite or acid sulphite, as, for
example, sodium sulphite, sodium acid sulphite,
etc. The hydrogenated abietyl halide dissolved in
a suitable solvent, as, for example, benzene,
xylene, petroleum hydrocarbonsrether, etc.“ will
be treated directly with the sulphite at. a suitable
temperature,‘ as, for example, from about 10° C.‘
to about 275° C. The use of a neutral sulphite
will produce directly the corresponding salt of
the sulphonated hydrogenated abietyl derivative, 70
thereof are substantially equivalent in the various while an acid sulphite will produce the usual
uses made 'ofthem, they will be referred to here'
acidic sulphonation product which will be neu
inafter and in the claims as sulphon'ation. prod tralized during its puri?cation.‘ If a hydrocarbon
ucts, which term is meant to include both sul
solvent is employed, the 'sulphonation product
phonates, sulphates and mixtures thereof‘.
will separate and can ‘be easily removed. If a 75
solvent in which it is soluble, e. g. ether, is used,
the product may be readily obtained by evapora
tion of the ether solution after its separation from
the insoluble salt formed in the reaction.
The procedure in accordance with this inven
tion for the production of sulphonated hydro~
genated abietyl derivatives is illustrated in its
more speci?c embodiments by the examples given
Example I
290 g. hydrogenated abietyl alcohol are mixed
and (c), the lower two phases comprising excess
H2304 and the solid sulphonic acids insoluble in
both hexane and H2804. Phase (a) is separated,
and the solvent evaporated, leaving a small
amount of sulphonic acids and some unsul
phonated material. To phases (b) and (c) are
added 200-250 cc. water with cooling and agita
tion. The sulphonated material, which is insolu
ble in 40-50% acid, separates and is combined
with that obtained from phase (a). The product 10
is then washed and neutralized as in Example I
with 120 g. acetic anhydride; to the mixture are ' to e?ect puri?cation.
slowly added 300 g. concentrated H2804 with cool
15 ing and vigorous agitation. The temperature is
held at about 10° C. while introducing the acid.
After the acid has been introduced, the agita
tion is continued at room temperature from 5 to
20 hours until complete water solubility results.
20 250 cc. water are then added with cooling and
, agitation, and the mixture allowed to stand. The
sulphonated material separates and is washed
with 500 cc. of 12% NaCl solution, then dissolved
in 200-300 cc. water and neutralized with 5%
NaOI-I. 300 cc. saturated salt solution are added
with agitation. The sodium salt of sulphonated
hydrogenated abietyl alcohol separates as a
brown-colored solid containing 642% sulphur,
possessing emulsifying, wetting and detergent
30 properties.
The above procedure may be varied in some
cases depending upon the type product desired.
For example: The alcohol may be added to the
sulphonating mixture. The temperature may be
35 raised, if it is desired to speed up reaction. The
amount of sulphonating acid and acetic anhy
dride used may also be varied depending upon
the degree of sulphonation desired. Other alka
lies and bases, as pyridine, etc., may be used in
40' neutralization, and the concentration of the base
used, whether inorganic or organic, may be wide
ly varied, for example, from 1 to 20%. The
amount and concentration of salt solution used
in the washing may likewise be widely varied.
Example II
290 g. hydrogenated abietyl alcohol are dis
solved in 600 g. ‘petroleum ether, and 116 g.
chlorsulphonic acid are added very slowly with
50 vigorous agitation while keeping the temperature
at 5-l0° C. If the acid is added slowly the sul
phonated material formed separates immediately
from the solvent. After all the acid is added, the
solvent is ?ltered from the sulphonated material.
55 Additional product remaining in the solvent may
be removed by evaporating the petroleum ether.
The product is puri?ed as in Example I.
The amount of solvent used may be widely
Also the temperature may vary widely,
60 as for example, from 0° to 50° C. The amount of
acid used, relative to the alcohol, may vary wide
ly, as for example, from the ratio of 0.2:1 to 5:1.
Other suitable saturated hydrocarbons such as
hexane, octane, etc. may be used as solvents.
Example III
290 g. hydrogenated abietyl alcohol are dis
solved in 290 g. hexane. 300 g. concentrated
H2804 are added slowly with vigorous agitation
70 while keeping the temperature at 10° C. to 20° C.
After the acid is added, the mixture is agitated
for ‘7-20 hours until complete sulphonation is
effected; Three phases will then be present: (a)
an upper phase consisting of hexane and some
76 sulphonated material emulsi?ed therein, and (b)
The amounts of reactants and solvent, and the
temperature may vary widely as in the other ex
Example IV
290 g. hydrogenated abietyl alcohol are slowly
added to 500 g. concentrated H2804 at 5-10° C.
with vigorous agitation. After the alcohol is add 20
ed, the mixture is agitated from 10-20 hours at
room temperature, until substantially complete
solubility in water results. 500 g. water is then
added with agitation and cooling. The sul
phonated material separates and is washed and 25
neutralized as in Example I. The ratio of alcohol
to acid used may vary from 1:03 to 1:20 depend
ing upon the type of product. By increasing the
temperature, the reaction rate may be increased,
at the expense of a light color however.
Example V
353 g. hydrogenated abietyl bromide are dis
solved in 350 g. octane;.126 g. anhydrous sodium
sulphite is added. The mixture is re?uxed for 8 35
hours with vigorous agitation. The solid material
is separated from the solvent and extracted with
warm butyl alcohol. The sodium hydrogenated
abietyl sulphonate is recovered by evaporation of
the butyl alcohol, while the sodium bromide
formed is left undissolved by this solvent.
The procedure may be modi?ed by heating the
reactants together at, for example, ‘IO-170° C. for
8 hours and then either extracting the solid ma
terial formed as before, or dissolving the entire 45
mixture in 300 cc. water and salting out the so—
dium sulphonate with NaCl, or the like. Other
non-reactive solvents, such as benzene, xylene,
terpineol, dipentene, pine oil. etc., are suitable'as
reaction media. When pine oil is used the sul
phonated material remains in the pine oil, while
the NaBr separates and may be removed by ?l
tration. The pine oil mixture may then be used
as an emulsive, dispersing, or wetting-out agent '
without further separation of sulphonated mate 55
rial. Various alcohols, esters and ethers may be
used as extraction solvents in place of butyl al
cohol, and the reaction may be carried out, if
desired, in such extraction solvents. Other sul
phites may be used in equivalent amounts.
Hydrogenated abietyl chloride may be substi
tuted for the bromide in molecular proportions.
If desired the various hydrogenated abietyl de
rivatives may be sulphonated in accordance with
this invention in admixture with various other 65
materials capable of sulphonation, as for ex
ample, lauryl alcohol, stearlyl alcohol, oleic,
stearic, linoleic acid, etc. The product in such
cases will be a mixed sulphonation product of
the materials used.
It will be appreciated that the method in ac
cordance with this invention is not limited to any
particular mode of procedure as shown in the
various examples, which are illustrative only, but
involves broadly only the treatment of a suitable 75
drogenated abietyl derivative which includes re-i
hydrogenated abietyl derivative witth a sulpho
nating agent. As has been said, the proportions of acting :a hydrogenated abietyl halide and a sui
phonating agent and extracting the; reaction
the amounts,
and the if
of of
be I. product with an inert solvent.
9. The sulphonation product of hydrogenated
widely varied to produce a material having the
properties desired'for any particular use er pur- W abietyl bromide.
10. The sulphonatiorl product of hydrogenated
Throughout this speci?cation and in the’claims
hereinafter set forth the following terms are ’
10 used with the following’meaning's:
abietyl chloride.
11. A sulph-onated derivative of hydroabietyl
alcohol having the formula Ab—CI-I2—SOa—-X 10
in which Ab is the hydrocarbon nucleus of hy
pounds of the type CraHzsCHzX, where X is a: droabietic acid and X is a material selected from
functional group. By the term “suitable hydro-I: the group consisting of hydrogen, alkali metals.
'genatediabietyl derivative” is meant a hydroi and ammonium.
“Abietyl derivative" refers to and includes com
15 genated abietyl derivative capable of reaction
tvith a sulphonating agent to give a sulphonated
" “Sulphonate”, and its grammatically related
forms, refer to and include the process ‘of sul
20, phonating and sulphatihg and/or the respective
sulphonates andf sulphates so formed or mixtures
What-"I claim and desire to protect by Letters
2Patent is:
1. The sulphonation product of a hydrogen-V
ated abietyl halide.
and ammonium.
13;;A sulphonated derivative of hydroabietyl
alcohol having the formula. Ab—CH21—§-SOa—-X in
which Ab is the hydrocarbon nucleus of tetra
hydrcabietio acid and X is Fa material selected
from the group consisting pf hydrogen, alkali 25.
metals and ammonium.
acting a hydrogenated cabietyl halide and a sul
14. A sulphonated; derivative of hydroabietyl
alcohol having the formula Ab—CHz—SO3—X
in which Ab is the hydrocarbon nucleus of hy
phonating agent.
droabietic acid and X is an alkali metal.
.2. The method of producing asulphonated hy=
drogenated abietyl derivative which includes re
12. A sulphonated derivative of hydroabietyl 15
alcohol having the formula Ab—CHz--SOa-—X in
'which Ab is the hydrocarbon nucleus of dihy
droabietic acid and Kris a material selected from
the group consisting ofhydrogen, alkali metals
3. The method of producing a sulphonated hy
drogenated abietyl derivative which includes re
1 acting a hydrogenated abietyl halide and a sui
15. A sulphonated derivative of hydroabietyl
alcohol having the formula Ab-CH2—SO3—X
in which Ab. is the hydrocarbon nucleus of dihy- '
droabietic acid and X is an; alkali metal. -
I 4. The method of producing a sulphoriated hy
drogenated abietyl derivative which includes re
16. A sulphonated derivative of hydroabietyl 35
alcohol having therformvula Ab——CH2—SO3—X
acting a hydrogenated: abietyl halide in solution
in which At;- is the hydrocarbon nucleus of tetra
hyroabietic acid and X is an alkali metal.
'in an inert solvent and a sulphonating agent.
5. The method of producing a sulphonated hy
40' drogenated abietyl derivative which includes re
acting a hydrogenated abietyl halide and sodium
1".7’. A sulphonated derivative of hydroabietyl
alcéhol having the formula Ab—CH2—SOa;-Na 40
in.which Ab is the hydrocarbon nucleus of hydro
abietic acid.
6. The method of producing a sulphcnated hy
" drogenated abietyl derivative which includes re
18. A suiphonated derivative of hydroabietyl
alcchol having the formula Ab—CH2—SOs—-Na
.acting a hydrogenated abietylforomide and a sul
phonating agent.
in which Ab is theghydrocarbon nucleus of dihy
droabietic acid.
19. A suiphonated derivativeyo'f hydroabietyl
alcohol having theiformula Ab—CHz--SOe—Na
acting a hydr-Qgenated abietyl chloride and a sul- , injljwhich Ab is the hydrocarbon nucleus of tetra
'7. The method of producing a sulphonated hy
drogenated ahietyl derivative which includes re
'50 ‘phonating
8. frhe method of producing asulphonated 5?
hydroabietic acid.
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